Process for the production of a yellow mask image in magenta-colored photographic images



V Ap fl 1959 BURGARDT EIAL 7 2,384,325

PROCESS FOR THE PRODUCTION OF A YELLOW MASK IMAGE IN MAGENTA-COLOREDPHOTOGRAPHIC IMAGES Filed-March 3, 1955 v EXPOSURE AND COLOR FORMING DEVELOPEMEN T NEGATIVE MAGENTA COLOR IMAGE PLUS SILVER 'IMAGE [REACT/0N-WITH PYRROLE ALDEHYDE POSITIVE YELLOW MASK/N6 IMAGE POSITIVE YELLOWMASK/N6 IMAGE I INVENTORS. .L OTHAR BURGARDT, EHCH RECKZIEGEL, OTTMARWAHL.

A TYTORNEYS United States Patent PROCESS FOR THE PRODUCTION OF A YELLOWMASK IMAGE IN MAGENTA-COLORED PHO- TOGRAPHIQ IMAGES Lothar Burgardt,Leverkusen-Bayerwerk, Erich Reckziegel, Leverknsen, and Ottmar Wahl,Opladen, Germany, assignors to Agfa Aktiengesellschaft Application March3, 1955, Serial No. 492,053

Claims priority, application Germany March 5, 1954 7 Claims. (Cl. 96-9)This invention relates to a process for the correction of photographiccolor images and more particularly to a process for the correction ofmagenta photographic images produced by the process of color formingdevelopment. It is known that azomethine dyes, which are generally usedfor the production of magenta-colored images according to the process ofcolor forming development, do not have a perfect absorption. They absorblight in the green range of the spectrum as well as some of the light inthe blue range of the spectrum. This fact obviously leads to a colordefect in the negative-positive process. This applies, for example, tomagenta dyestuffs which are formed by color-forming development frompyrazolones. It is also known that it is possible to compensate for thisundesirable secondary absorption in the blue range of the spectrum bymeans of a masking image, the absorption of which corresponds to thesecondary absorption of the said negative image.

Such masking images may be produced by transforming the color couplerscontained in a silver halide layer after color forming development intoyellow dyestuffs. For this purpose, a process has already been proposedwhich is characterised in that the light-sensitive material, whichcontains a diffusion-resisting pyrazolone or a similar compoundcontaining an active methylene group as magenta color-former, is treatedafter exposure and color development with an aromatic aldehyde of thebenzene or naphthalene series which contains an auxochromic group, orwith a functional derivative of such an aldehyde. The residual colorcoupler in such a case is transformed by the aldehyde to form a yellowdyestulf, which serves as a color mask for correcting the undesiredsecondary absorption of the image dye. Appropriate compounds forcarrying out this process are monoand di-substitutedp-aminobenzaldehydes and the anils, arylhydrazones or bisulphitereaction products of such aldehydes, which are alkali-soluble as aresult of suitable substituents, for example, sulphonic groups. Theyellow masking image dyes obtained by this process have thedisadvantage, however, that their absorption is not restricted to theblue part of the spectrum, but also extend to the green part thereof.However, an undesirable flattening of the gradation of the magenta imagedyestufi is caused by this absorption in the green part of the spectrum.

It has now been found that for the production of yellow masking imagesfor magenta-colored images produced in photographic layers containingcolor couplers by the method of color forming development, it ispossible with particular advantage to use aldehydes of pyrrole, indoleand carbazone and their functional derivatives, more especially theanils of these aldehydes.

These aldehydes are particularly suitable, because they lead to styryldyestuffs, which are of shorter wavelength in their absorption than thecorresponding dyes with substituted aminobenzaldehydes and thereforecannot be the cause of a disadvantageous flattening in the gradation ofthe magenta dyestufi image.

; ample,

The aforementioned heterocyclic aldehyes are particularly valuable forthe purpose in question, because the use thereof, independently of theduration of their action on the photographic material does not lead toovermasking, i.e. a positive yellow image with higher density than thatof the secondary absorption of the magenta image dyestuffs formed frompyrazolones. The secondary absorptions of these magenta image dyestuffsand the yellow masking dyes which are formed have in fact substantiallythe same color density.

The production of the said aldehydes is carried out in accordance withknown processes. Pyrrole aldehydes, indole aldehydes and N-substitutedcarbazole aldehydes are adapted to be manufactured easily with goodyields according to the method of Vilsmeier and Haack (Berichte derdeutschen chemischen Gesellschaft 60, 119). Pyrrole aldehydes and indolealdehydes are also available by other methods, for example, the Reimer-Tiemann synthesis (for example, Berichte der deutschen chemischenGesellschaft 61, 1078). By treatment of suitable aldehydes withconventional sulphonating agents, it is possible for sulphonic acids tobe prepared therefrom. Examples of suitable aldehydes which may bementioned, inter alia, are: u-pyrrole aldehyde,2.4-diphenylpyrrole-S-aldehyde, ,G-indole aldehyde, indole-3-aldehyde-carboxylic acid, 1-methyl-2-phenylindole-3- aldehyde, N-(carboxyethyl)-carbazole-3-aldehyde, N-ethyl-carbazole-3-aldehyde-sulphonic acid andN-ethylcarbazole-3-aldehyde. The anils are produced according to knownprocesses. Particularly suitable for this purpose are those anilinederivatives which carry positive substituents, such as, for example,hydroxy-, alkoxyor dialkylamino-groups. Sparingly soluble aldehydes, onthe other hand, are transformed into alkali-soluble compounds byreaction with aniline-sulphonic acids.

The process according to the invention is particularly suitable for theproduction of yellow masking images in photographic multi-layermaterials which contain color couplers for the production of yellow,magenta and cyan color couplers in three superimposed silver halidelayers which are sensitive to diflferent regions of the spectrum.Appropriate couplers for the production of magneta images are the wellknown pyrazolones-S, for ex- 1(4-phenoxy-5-sulphophenyl)-3-heptadecyl-5- pyrazolone. There may also beused other couplers such as cyanacetyl compounds. The process isillustrated in the accompanying drawing and is further explained by thefollowing examples.

Example 1 The following multi-layer light sensitive material is used:

A transparent support is coated with a layer of a red sensitive silverhalide emulsion containing 20 grams per litre of the cyan color formingcoupler having the formula:

CH3.N. 0171135 OH NH.OO

SO H

Upon this layer there is applied a layer of a green sensitive silverhalide emulsion layer containing per litre 15 grams of the magenta colorforming coupler 1-(4- phenoxy'sulphophenyl)-3-heptadecyl-5-pyrazolone.On this layer a yellow filter layer of colloidal silver and thereupon anoptically not sensitized silver halide layer 3 is coated, which containsper litre the following yellow color forming coupler:

This film is exposed to an object to be reproduced and developed in adeveloper solution of the following composition:

COOH

OOH

Diethyl-p-phenylene-diamine-hydrochloride 3 g.

After rinsing, the material is bathed in an 0.5% slightly alkalinesolution of m-"nethoxy-anil of fl-indolealdehyde- 2-carboxylic acid. Thefilm is then bleached, fixed and washed in the conventional manner. Thematerial thus treated now contains a positive yellow color image servingas a mask in the green-sensitive layer, in addition to its cyan, magentaand yellow negative component images. The ,B-indolealdehyde-Z-carboxylicacid is obtained from e-indole-carboxylic acid ethyl ether according tothe process disclosed in J. Am. Chem. Soc. 68 (1946), 1156.

Example 2 Instead of the said solution of m-methoxy-anil of [3-indole-aldehyde-Z-carho-xylic acid referred to in Example 1, there mayequally well be employed an 0.5-1% weakly alkaline solution ofm-dimethyl amino-anil of N-ethylcarbazole-3-aldehyde-sulphonic acid forthe production of the yellow masking image.

N-ethyl-carbazole-3-aldehyde sulphonic acid is obtained in the followingmanner:

To a mixture of 1.1 mols of N-formyl-N-methylaniline and 2 mols ofphosphoroxychloride there are 'added by degrees while stirring 1 mol ofN-ethylcarhazole. The reaction mixture is kept for 12 hours at 3035 C.and thereafter introduced into water at 40-45 C. The oil formed isstirred until crystallization takes place. The reaction product isisolated and recrystallized from ethanol.

Yield of N-ethylcarbazolaldehyde, 200 g. RP. 81 C.

700 g. of N-ethylcarbazolaldehyde are sulfonated with a mixture of 1.7litres of concentrated sulphuric acid and 300 mol of oleum 20% at C.

Example 3 Instead of the said solution of m-methoxy-anil offi-indole-aldehyde-Z-carboxylic acid referred to in Example 1, there isemployed an 0.5 Weakly alkaline solution of m-hydroxyanil of ot-pyrrolealdehyde for the production of the masking image. The a-pyrrol-aldehydeis obtained according to the process disclosed in Berichte der-Deutschen Chemischen Gesellschaft 51 (1928), 1078.

Example 4 A multi-layer material, in which the bottom red-sensitivesilver halide layer with blue-green component has coated thereon agreen-sensitive silver halide layer with yellow component, above whichis a yellow filter layer and an unsensitised silver halide layer with apyrazolone as magenta dyestuif former, is exposed and developed as inExample 1.

After being rinsed, the material is treated with an 0.5-1% weaklyalkaline solution of the m-sulphanil of N- ethyl-carbaZole-3-aldehyde,bleached, fixed and washed. In addition to the negative blue-green andyellow images in the bottom coating and middle coating, the film nowcontains a negative magenta image in the top coating, opposite-whichis ayellow masking image.

4 Example 5 Instead of the solution mentioned in Example 4 for theproduction of a yellow masking image, there may equally well be employeda weakly alkaline solution of a sulphanil of1-methyl-2-phenyl-indole-3-aldchyde. This aldehyde is obtained by theprocess disclosed in German patent specification 614,325.

Example 6 Instead of the solution mentioned in Example 4, the maskingimage may be produced by using the weakly alkaline solution ofm-hydroxyanil of 2.4-diphenyl-pyrrol- S-aldehyde. This aldehyde isobtained by the process disclosed in J. Chem. Soc. (London) 1943, p.596.

Any other theoretically possible arrangement or association of thelayers may be chosen for this process, apart from the multi-layermaterials described in the examples.

Example 7 For the production of a duplicate negative, three positiveblack-and-white separation records produced from a multi-color negativeare successively exposed by means of three partial color record filterson to a multi-layer material which has a bottom red-sensitive silverhalide layer with a cyan color forming coupler, above this agreensensitive silver halide layer with a yellow color forming couplerand a top layer of an unsensitised silver halide layer with a pyrazoloneas magneta color forming coupler, all layers containing tartrazinc asfilter dyestutf instead of using a separate filter layer. The colorforming couplers may be the same as those disclosed in Example 1. Thematerial thus exposed is developed in a developer of the followingcomposition:

Diethyl-p-phenylene-diamine-hydrochloride g 3 Anhydrous soda g 60Potassium bromide g 2 Anhydrous sodium sulphite g 2 Water cc 1,000

is thereafter rinsed and bathed in an 0.5 Weakly alkaline solution ofp-sulphanil of B-indole aldehyde (see I. Am. Chem. Soc. 68 (1946), p.1156). After bleaching, fixing and rinsing, the multi-layer materialcontains a negative blue-green image in the bottom coating, a negativeyellow image in the middle coating and a negative magenta image with ayellow masking image in the top coating.

What we claim is:

1. A process for the production of a yellow masking image for amagenta-colored image comprising develop ing an imagewise-exposed silverhalide emulsion layer, containing a magenta color-forming coupler havingan active methylene group, with a primary aromatic amino developingagent to form a magenta dye image, and reacting the residualcolor-forming coupler with an aldehyde to produce a yellow styryldyestufi masking image, said aldehyde being selected from the groupconsisting of pyrrolealdehydes, indole-aldehydes, carbazole aldehydesand anils thereof.

2. The process of claim 1 wherein the magenta colorforming coupler is apyrazolone.

3. A process for the production of a yellow masking image for amagenta-colored image which comprises developing an imagewise-exposedphotographic material comprising a transparent base and a plurality ofsuperimposed silver halide emulsion layers coated on said base, one ofsaid layers containing a magenta-color-forming coupler having an activemethylene group, with a primary aromatic amino developing agent to forma magenta dye image in said layer containing said magenta color-formingcoupler, and reacting the residual colorforming coupler with an aldehydeto produce a yellow styryl dyestuif image, said aldehyde being selectedfrom the group consisting of pyrrole aldehydes, indole aldehydes,carbazole aldehydes and anils thereof,

5 6 4. The process of claim 3 wherein one of said layers 7. The processof claim 1 wherein said aldehyde concomprises a red-sensitive silverhalide layer containing a (aims a Sulfonic acid group bonded to a cycliccarbon cyan color-forming coupler, another of said layers comatomprlsesa green-sensitwe sllver halide layer sltuated above References Cited inthe file of this patent said red-sensitive layer, and a third layercomprises an 5 unsensitized silver halide layer situated above saidgreen- UNITED STATES PATENTS sensitive layer, one of said last-mentionedlayers con- 1,731,966 Ballauf 0 taining pyrazolone as a magentacolor-forming coupler. 1,398,445 e Z et a1. Feb. 21, 1933 5. The processof claim 1 wherein said aldehyde con- 10 1,954,452 Mannes et P 1934tains a hydroxyl group bonded to a cyclic carbon atom. 2,252,718 Manneset 191 1941 6. The process of claim 1 wherein said aldehyde congsgg ii.

tams a carboxyl group bonded to a cycllc carbon atom. 2,704709 p g Mar.1955

1.A PROCESS FOR THE PRODUCTION OF A YELLOW MASKING IMAGE FOR AMAGENTA-COLORED IMAGE COMPRISING DEVELOPING AN IMAGEWISE-EXPOSED SILVERHALIDE EMULSION LAYER, CONTAINING A MAGENTA COLOUR-FORMING COUPLERHAVING AN ACTIVE METHYLENE GROUP, WITH A PRIMARY AROMATIC AMINODEVELOPING AGENT TO FORM A MEGENTA DYE IMAGE, AND REACTING THE RESIDUALCOLOR-FORMING COUPLER WITH AN ALDEHYDE TO PRODUCE A YELLOW STYRYLDYESTUFF MASKING IMAGE, SAID SLDEHYDE BEING SELECTED FROM THE GROUPCONSISTING OF PYRROLEADLDSHYDES, INDOLE-ALDEHYDES, CARBAZOLE ALDEHYDESAND ANILS THEROF.